CN106207261A - Electrolyte and battery - Google Patents

Electrolyte and battery Download PDF

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Publication number
CN106207261A
CN106207261A CN201610172101.6A CN201610172101A CN106207261A CN 106207261 A CN106207261 A CN 106207261A CN 201610172101 A CN201610172101 A CN 201610172101A CN 106207261 A CN106207261 A CN 106207261A
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China
Prior art keywords
electrolyte
alkali metal
nonaqueous solvent
battery
active material
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CN201610172101.6A
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CN106207261B (en
Inventor
中堤贵之
前西真弓
北条伸彦
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The problem of the present invention is, in the prior art, it is desirable to realize the battery that reliability is high.Solution is a kind of electrolyte, and containing nonaqueous solvent and the alkali metal salt being dissolved in nonaqueous solvent, described nonaqueous solvent contains the chain carboxylate shown in formula (1).Wherein, R1 and R2 separately represents aromatic series base or unsaturated aliphatic base or representative examples of saturated aliphatic base.And, a kind of battery, possess above-mentioned electrolyte, positive pole and negative pole, described positive pole contains energy occlusion and the positive active material of release alkali metal ion, and described negative pole contains energy occlusion and the negative electrode active material of release alkali metal ion or containing alkali metal.

Description

Electrolyte and battery
Technical field
It relates to the electrolyte of battery and battery.
Background technology
Patent Document 1 discloses a kind of battery with nonaqueous electrolyte, it possesses use containing carbonic acid Asia second The nonaqueous electrolytic solution of the solvent of ester.
Prior art literature
Patent documentation
Patent documentation 1:(Japan) Unexamined Patent 10-289731 publication
Summary of the invention
Invent problem to be solved
In prior art, it is desirable to realize the battery that reliability is high.
For solving the means of problem
The electrolyte of one embodiment of the disclosure contains nonaqueous solvent and is dissolved in the alkali of nonaqueous solvent Slaine, described nonaqueous solvent contains the chain carboxylate shown in formula (1).Here, in formula (1) R1 and R2 separately represents aromatic series base or unsaturated aliphatic base or representative examples of saturated aliphatic base.
Invention effect
According to the disclosure, it is possible to achieve the battery that reliability is high.
Accompanying drawing explanation
Fig. 1 is the schematic perspective view of an example of the battery illustrating embodiment 2.
Fig. 2 is the schematic sectional view of an example of the battery illustrating embodiment 2.
Fig. 3 is the figure of the schematic configuration illustrating the battery lead plate in embodiment 1.
Fig. 4 is the axonometric chart of the schematic configuration illustrating the battery in embodiment 1.
Description of reference numerals
10 positive poles
1a positive electrode material mixture layer
1b positive electrode collector
1c positive pole ear goes between
20 negative poles
2a anode mixture layer
2b negative electrode collector
2c negative lug goes between
30 barrier films
4 pole plate groups
5 shells
6 insulation tab films
Detailed description of the invention
Hereinafter, embodiment of this disclosure illustrates.
First, below the starting point of present inventor is illustrated.
Such as, as being equipped on the battery of automobile etc., even if needing the most also to have high Reliability.That is, it needs to have higher than the solvent of prior art under high temperature (such as more than 60 DEG C) environment The solvent of reliability.
Based on the above starting point, present inventor finally creates the composition of the disclosure.
(embodiment 1)
The electrolyte of embodiment 1 contains nonaqueous solvent and is dissolved in the alkali metal salt of nonaqueous solvent.
Nonaqueous solvent contains the chain carboxylate shown in following formula (1).
Here, R1And R2Separately represent aromatic series base or unsaturated aliphatic base or saturated fat Fat race base.
According to above composition, even if the electrolyte of embodiment 1 is at a temperature of height, at positive pole and Also stablize on negative pole.That is, the electrolyte of embodiment 1 has high reliability.Thus, it is possible to it is real The battery that existing reliability is high.
As shown in following formula (2), generally, in carboxylate, the hydrogen of α position is easily by one-electron reduction Remove.
Therefore, reaching when charging on the negative pole of low current potential, carboxylate is susceptible to continuous print reduction Decompose.Particularly, under the high temperature more than 60 DEG C, this reaction is promoted.
On the other hand, the chain carboxylate shown in above-mentioned formula (1) does not have hydrogen in α position, therefore, recognizes Improve for reducing resistance.Think owing to such former reliability that thus results in improves.
It addition, carboxylate and carbonic ester, reach on the positive pole of high potential when charging, single electron occurs Oxidation decomposition, produces CO2Deng gas.Particularly, under the high temperature more than 60 DEG C, this reaction quilt Promote.
On the other hand, when the chain carboxylate generation one-electron oxidation shown in above-mentioned formula (1), adjoint The open loop of cyclopropyl, generates radical cation.By the polyreaction of this radical cation, raw Become the polymer insoluble in electrolyte.Speculate that this polymer is piled up in positive electrode surface.Think this positive pole table The polymer protection positive electrode surface in face.Thus, it is believed that the continuous print oxidation Decomposition of electrolyte is suppressed. Think owing to such former reliability that thus results in improves.
Additionally, the R in above-mentioned formula (1)1And R2It can also be mutually the same substituent group.
Or, the R in above-mentioned formula (1)1And R2It can also be substituent group different from each other.
Alternatively, it is also possible to be R1Or R2In the composition that replaced by fluorine of the part of hydrogen atom.
As the chain carboxylate shown in above-mentioned formula (1), R can be used1And R2It is the 1-first of methyl Basic ring propane-1-methyl formate, R1For methyl and R2For ethyl 1-methyl cyclopropane-1-Ethyl formate, R1For ethyl and R21-ethyl cyclopropane-1-methyl formate, R for methyl1For ethyl and R2For second The 1-ethyl cyclopropane-1-Ethyl formate of base, R1For vinyl and R21-ethylene basic ring third for methyl Alkane-1-methyl formate, R1For methyl and R2For vinyl 1-methyl cyclopropane-1-vinyl formate, R1For phenyl and R21-cyclo-propane-1-methyl formate, R for methyl1For methyl and R2For benzene 1-methyl cyclopropane-1-the phenyl formate of base, R1For trifluoromethyl and R21-trifluoromethyl for methyl Cyclopropane-1-methyl formate, R1For methyl and R21-methyl cyclopropane-1-formic acid three for trifluoromethyl Fluorine methyl ester etc..They can be used alone.Or they can also combine two or more use.
Here, in the electrolyte of embodiment 1, the R of chain carboxylate1And R2First can be Base.
That is, in the electrolyte of embodiment 1, chain carboxylate can also be 1-methyl cyclopropane-1- Methyl formate.
According to above composition, the ionic conductance (ionic conductance) of electrolyte can be improved.
Nonaqueous solvent is in addition to the chain carboxylate shown in above-mentioned formula (1), it is also possible to containing other non-aqueous Agent.
As other nonaqueous solvent, the known solvent for nonaqueous electrolytic solution can be used.Specifically, As other nonaqueous solvent, can use cyclic carbonate, linear carbonate, cyclic carboxylic esters, non-on State the chain carboxylate shown in formula (1), chain nitrile, cyclic ether, chain ether etc..
Containing in the case of cyclic carbonate in nonaqueous solvent, the ionic conduction of electrolyte can be improved Rate.As cyclic carbonate, can use ethylene carbonate, fluoroethylene carbonate, propylene carbonate, Butylene carbonate, vinylene carbonate, vinyl ethylene carbonate and their derivant etc..It Can be used alone.Or can also be combined two or more use.Use selected from ethylene carbonate, In the case of at least one in fluoroethylene carbonate, propylene carbonate, electrolyte can be improved Ionic conductivity.In the case of using fluoroethylene carbonate, electrolyte can be improved on negative pole Stability.
That is, in the electrolyte of embodiment 1, nonaqueous solvent can also contain fluoroethylene carbonate.
According to above composition, the ionic conductance of electrolyte can be improved.Furthermore it is possible to improve electricity Solve liquid stability on negative pole.
As linear carbonate, can use dimethyl carbonate, Ethyl methyl carbonate, diethyl carbonate and it Derivant etc..As their derivant, a part for hydrogen for above-mentioned carbonic ester can be used by fluorine The fluoro body that instead of.In the case of using fluoro body, the stability on positive pole can be improved. They can be used alone.Or can also be combined two or more use.
As cyclic carboxylic esters, gamma-butyrolacton, gamma-valerolactone and their derivant etc. can be used.Make For their derivant, the compound that a part for hydrogen be instead of by fluorine can be used.Using this chemical combination In the case of thing, oxidative resistance can be improved.They can be used alone.Or 2 can also be combined Plant used above.
As the chain carboxylate shown in above-mentioned non-formula (1), can enumerate methyl acetate, ethyl acetate, Propyl acetate, methyl propionate, ethyl propionate, propyl propionate and their derivant etc..As them Derivant, the compound that a part for hydrogen be instead of by fluorine can be used.In the feelings using this compound Under condition, oxidative resistance can be improved.They can be used alone.Or can also be combined two or more Use.
As chain nitrile, can use acetonitrile, propionitrile, butyronitrile, valeronitrile, isopropyl cyanide, trimethylacetonitrile, oneself Dintrile, pimelic dinitrile and their derivant etc..As their derivant, a part for hydrogen can be used The compound that be instead of by fluorine.In the case of using this compound, oxidative resistance can be improved.It Can be used alone.Or can also be combined two or more use.
As cyclic ether, DOX, Isosorbide-5-Nitrae-dioxolanes, oxolane, 2-methyl can be used Oxolane and their derivant etc..As their derivant, a part for hydrogen can be used by fluorine The compound that instead of.In the case of using this compound, oxidative resistance can be improved.They can To be used alone.Or can also be combined two or more use.
As chain ether, 1 can be used, 2-dimethoxy-ethane, dimethyl ether, Anaesthetie Ether, dipropyl Base ether, ethyl-methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol two Butyl ether and their derivant etc..As their derivant, a part for hydrogen can be used to be taken by fluorine The compound in generation.In the case of using this compound, oxidative resistance can be improved.They are permissible It is used alone.Or can also be combined two or more use.
As being dissolvable in water the alkali metal salt of nonaqueous solvent, lithium salts, sodium salt etc. can be used.
As lithium salts, LiClO can be used4、LiBF4、LiPF6、LiN(SO2F)2、LiN(SO2CF3)2、 Dioxalic acid Lithium biborate (LiBOB) etc..
As sodium salt, NaClO can be used4、NaBF4、NaPF6、NaN(SO2F)2、NaN(SO2CF3)2 Deng.
Here, in the electrolyte of embodiment 1, alkali metal salt can be lithium salts.
Now, lithium salts can be selected from LiBF4、LiPF6、LiN(SO2CF3)2And LiN (SO2F)2 In at least one.
According to above composition, the ionic conductance of electrolyte can be improved.
Additionally, the molar content of the alkali metal salt in electrolyte can be such as more than 0.5mol/L and 2.0mol/L below.
Additionally, in the electrolyte of embodiment 1, relative to the cumulative volume of nonaqueous solvent, chain carboxylic The ratio of acid esters can be 1 more than volume %.
According to above composition, it is possible to achieve the battery that reliability is high.
It addition, in the electrolyte of embodiment 1, relative to the cumulative volume of nonaqueous solvent, chain carboxylic The ratio of acid esters can be 50 more than volume %.
According to above composition, it is possible to achieve the higher battery of reliability.
It addition, in the electrolyte of embodiment 1, relative to the cumulative volume of nonaqueous solvent, chain carboxylic The ratio of acid esters can be 80 more than volume %.
According to above composition, it is possible to achieve the higher battery of reliability.
(embodiment 2)
Hereinafter, embodiment 2 is illustrated.Additionally, the explanation repeated with above-mentioned embodiment 1 Suitable omission.
The battery of embodiment 2 possesses electrolyte, positive pole and the negative pole of above-mentioned embodiment 1.
Positive pole contains can occlusion and the positive active material of release alkali metal cation.
Negative pole contains energy occlusion and the negative electrode active material of release alkali metal cation, or containing alkali gold Belong to.
According to above composition, it is possible to achieve even if the most also having the electricity of high reliability Pond.
The battery of embodiment 2 is such as configured to secondary cell.
It addition, in the battery of embodiment 2, negative pole can contain alkali metal.Now, this alkali metal It can be lithium.
According to above composition, it is possible to achieve improve the electricity of the battery behavior such as energy density or reliability Pond.
It addition, in the battery of embodiment 2, negative pole can contain negative electrode active material.Now, should Negative electrode active material can be carbon.
According to above composition, it is possible to achieve improve the electricity of the battery behavior such as energy density or reliability Pond.
It addition, in the battery of embodiment 2, positive active material can be containing selected from nickel, cobalt, At least one element in manganese and the metal-oxide of lithium.
According to above composition, it is possible to achieve improve the electricity of the battery behavior such as energy density or reliability Pond.
Fig. 1 is the schematic perspective view of an example of the battery illustrating embodiment 2.
Fig. 2 is the schematic cross sectional views of an example of the battery illustrating embodiment 2.
As shown in Figures 1 and 2, the battery of embodiment 2 possesses pole plate group 4 and shell 5.
Pole plate group 4 is housed inside in shell 5.
Pole plate group 4 has positive pole 10, negative pole 20 and barrier film 30.
Positive pole 10 is made up of positive electrode collector 1b and positive electrode material mixture layer 1a.
Positive electrode material mixture layer 1a is formed on positive electrode collector 1b.
Negative pole 20 is made up of negative electrode collector 2b and anode mixture layer 2a.
Anode mixture layer 2a is formed on negative electrode collector 2b.
Positive pole 10 and negative pole 20 are opposed across barrier film 30.Thus, pole plate group 4 is formed.
Containing the electrolyte being soaked with embodiment 1 in pole plate group 4.
On positive electrode collector 1b, connection has positive pole ear lead-in wire 1c.
On negative electrode collector 2b, connection has negative lug lead-in wire 2c.
Positive pole ear lead-in wire 1c and negative lug lead-in wire 2c extends respectively into outside shell 5.
Insulation tab film 6 it is configured with between positive pole ear lead-in wire 1c and shell 5.
Insulation tab film 6 it is configured with between negative lug lead-in wire 2c and shell 5.
Positive electrode material mixture layer 1a contains can occlusion and the positive active material of release alkali metal ion.
As positive active material, for can occlusion and discharge the material of one or more alkali metal ions. Such as, as positive active material, can use containing alkali-metal transition metal oxide, transition gold Belong to fluoride, polyanionic material, fluorination polyanionic material, transient metal sulfide etc..Such as, As positive active material, Li can be usedxMeyO2And Li1+xMeyO3(0 ＜ x 1,0.95 y ＜ 1.05, Me comprise in Co, Ni, Mn, Fe, Cr, Cu, Mo, Ti and Sn at least A kind of) etc. lithium-containing transition metal oxide.Or, as positive active material, can use LixMeyPO4And LixMeyP2O7(0 ＜ x 1,0.95 y ＜ 1.05, Me comprise selected from Co, Ni, At least one in Mn, Fe, Cu, Mo) etc. containing lithium polyanionic material.Or, as positive pole Active substance, can use NaxMeyO2(0 ＜ x 1,0.95 y ＜ 1.05, Me comprise selected from Co, At least one in Ni, Mn, Fe, Cr, Cu, Mo, Ti and Sn) etc. containing sodium oxo transition metal Compound.
As positive electrode collector 1b, can use by gold such as aluminum, aluminium alloy, rustless steel, titanium, titanium alloys Belong to Porous or the sheet material of atresia or film that material makes.Aluminum or its alloy are being used as positive electrode collector In the case of the material of 1b, it is cheap, and easily filming.As sheet material or film, gold can be used Belong to paper tinsel, wire netting etc..For reduce resistance value purpose or give catalyst effect purpose or The purpose of the combination etc. of strengthening positive electrode material mixture layer 1a and positive electrode collector 1b, can be at positive electrode collector The material with carbon elements such as carbon it are coated with on the surface of 1b.
Anode mixture layer 2a contains can occlusion and the negative electrode active material of release alkali metal ion.
As negative electrode active material, occlusion and the material of release alkali metal ion or alkali metal can be used. As occlusion and the material of release alkali metal ion, alkali metal alloy, carbon, oxo transition metal can be used Compound, silicon materials etc..Such as, as the negative material of lithium secondary battery, can use selected from Zn, The alloy of the metal in Al, Sn, Si, Pb, Na, Ca, In, Mg and lithium or Delanium, Native graphite, difficult carbon or the Li such as graphitization amorphous carbon, easy graphitization amorphous carbon4Ti5O12、 TiO2、V2O5Deng transition metal oxide or SiOx(0 ＜ x 2), lithium metal etc..It addition, Such as, as the negative material of sodium rechargeable battery, can use selected from Zn, Al, Sn, Si, Pb, Metal in Na, Ca, In, Mg and the alloy of sodium or difficult graphitization amorphous carbon, easy graphite Change carbon or the Na such as amorphous carbon2Ti3O7、Na2Ti6O13Deng transition metal oxide or sodium gold Belong to.
As negative electrode collector 2b, can use by aluminum, aluminium alloy, rustless steel, nickel, nickel alloy, copper, Porous that the metal material such as copper alloy makes or the sheet material of atresia or film.Aluminum or its alloy are being used as In the case of the material of negative electrode collector 2b, it is cheap, and easily filming.As sheet material or Film, can use metal forming, wire netting etc..For reducing the purpose of resistance value or giving catalyst effect The purpose of fruit or the purpose of the combination etc. of strengthening anode mixture layer 2a and negative electrode collector 2b are permissible The surface of negative electrode collector 2b is coated with the material with carbon elements such as carbon.
As barrier film 30, can use and be made by polyethylene, polypropylene, glass, cellulose, pottery etc. Multiple aperture plasma membrane.Such as, the inside at the pore of barrier film 30 is impregnated with electrolyte.
Positive electrode material mixture layer 1a and anode mixture layer 2a can also containing conductive auxiliary agent or ion-conducting material, Or binding agent.
As conductive auxiliary agent, material with carbon element, polyaniline, the poly-pyrroles such as white carbon black, graphite, acetylene black can be used Cough up, the electroconductive polymer etc. such as polythiophene.
As ion-conducting material, polymethacrylates, polymethyl methacrylate isogel can be used The solid electrolyte such as electrolyte, poly(ethylene oxide) etc..
As binding agent, polyvinylidene fluoride, vinylidene difluoride-hexafluoropropylene copolymer, partially can be used Difluoroethylene-TFE copolymer, politef, carboxymethyl cellulose, polyacrylic acid, benzene second Alkene-butadiene copolymer rubber, polypropylene, polyethylene, polyimides etc..
As conductive auxiliary agent, ion-conducting material, binding agent, generally well-known material can be used respectively.
The shape of the battery of embodiment 2 can also be flap-type, Coin shape, button type, lamination-type, The types such as cylinder type, inclined flat pattern, square.
Embodiment
Hereinafter, embodiment of this disclosure illustrates.But, the composition of the disclosure is not limited to Embodiments described below.
＜ embodiment 1 ＞
[modulation of nonaqueous electrolytic solution]
114435-02-8) and 1-methyl cyclopropane-1-formic acid first at fluoroethylene carbonate, (CAS numbers: (CAS numbers ester: dissolve 1.0mol/L's in mixed solvent (volume ratio 1:4) 6206-25-3) LiPF6(CAS numbers: 21324-40-3), make electrolyte.
[making of positive plate]
First, as positive active material, prepare Li (Ni, Co, Al) O2.At 100 weight portions Positive active material mixes acetylene black 5 weight portion as conductive agent, as poly-inclined the two of binding agent Fluoroethylene resin 5 weight portion.Make them be scattered in dehydration METHYLPYRROLIDONE, modulate pulping The anode mixture of material shape.This anode mixture is only coated the positive pole being made up of the aluminium foil of thickness 15 μm The one side of collector body.Roll after being dried, obtain positive plate.Dried anode mixture is coated with Cloth amount is 10mg/cm2。
[making of negative plate]
Delanium powder 98 weight portion, SBR styrene butadiene rubbers 1 weight portion and carboxymethyl is fine Tie up plain 1 weight portion mixing.Make them be dispersed in water, be modulated into the cathode agent of pulp-like.Should Cathode agent only coats the one side of the negative electrode collector being made up of the Copper Foil of thickness 10 μm.Done Roll after dry, obtain negative plate.Dried cathode agent coating weight is 6.5mg/cm2。
[making of small disc type batteries]
Fig. 3 is the figure of the schematic configuration of the battery lead plate illustrating embodiment 1.
Fig. 4 is the axonometric chart of the schematic configuration of the battery illustrating embodiment 1.
First, positive plate and negative plate are processed into the composition shown in Fig. 3.As for electrode area, just Pole and negative pole are 24cm2.Lug as positive pole goes between, and uses the lug lead-in wire of aluminum.Make Lug for negative pole goes between, and uses the lug lead-in wire of nickel.Lug lead-in wire is deposited with thermally welded Resin.As shown in Figure 4, positive plate and negative plate across barrier film (polypropylene system, thickness 30 μm) with electricity The mode that pole overlaps each other is opposed.
Then, the rectangular aluminum laminate sheet (thickness 100 μm) that will be cut into 120 × 120mm folds. By the end face of its 120mm with 230 DEG C of heat seals.It is made into the tubular of 120 × 60mm.From 60mm End face put into the most opposed electrode group.The end face of aluminum laminate sheet is gone between with lug The position para-position of thermally welded resin, and with 230 DEG C of heat seals.
Then, the nonaqueous electrolytic solution of 0.8cc is injected from the unencapsulated side of laminate.After fluid injection 15 minutes are stood under the vacuum of 0.06MPa.Thus, electrolyte is made to be impregnated in inside electrode composition.
Finally, by the end face of the laminate of the side that carries out fluid injection with 230 DEG C of heat seals.
[evaluation of battery]
Evaluate the battery of above-mentioned making in the following order.
When being evaluated, clamp above laminate with the corrosion resistant plate (thickness 2mm) of 80 × 80cm Battery lead plate, and battery is pressurizeed with 0.2MPa with the fixture of U font.
First, in the temperature chamber of 25 DEG C, repeat the charging in 3 cycles with the constant current of 1mA and put Electricity.Charge with cell voltage for stopping during 4.2V, discharge with cell voltage for stopping during 2.5V.Fill It it is 20 minutes between electricity and electric discharge, with standing of opening a way.
Then, in the temperature chamber of 25 DEG C, with the constant-current charge of 5mA to 4.2V.Afterwards, keep In the constant voltage of 4.2V, till current value is less than 1mA.After standing 20 minutes under open circuit, With the constant-current discharge of 1mA to 2.5V in the temperature chamber of 25 DEG C.Now, measure discharge capacity, will This discharge capacity is designated as " capacity before high-temperature charging ".
Then, in the temperature chamber of 60 DEG C, crossing current with 5mA charges to 4.2V.Then, with 4.2V Constant voltage trickle charge 72 hours.Afterwards, make temperature chamber revert to 25 DEG C, under open circuit, keep 1 Hour.Afterwards, with the constant-current discharge of 1mA.Now, discharge capacity is measured, by this discharge capacity It is designated as " capacity after high-temperature charging ".
Calculate above-mentioned " capacity after the high-temperature charging " ratio relative to " capacity before high-temperature charging ", be designated as " holding Amount sustainment rate ".Index as reliability.The results are shown in table 1.
＜ embodiment 2 ＞
The solvent of electrolyte uses fluoroethylene carbonate and dimethyl carbonate and 1-methyl cyclopropane-1- The mixed solvent (volume ratio 20:79:1) of methyl formate.
In addition, in the way of similarly to Example 1, battery is made.Afterwards, with embodiment 1 Same mode carries out the evaluation of this battery.The results are shown in table 1.
＜ comparative example 1 ＞
As the solvent of electrolyte, use fluoroethylene carbonate and dimethyl carbonate (CAS numbers: Mixed solvent (volume ratio 1:4) 616-38-6).
In addition, in the way of similarly to Example 1, battery is made.Afterwards, with embodiment 1 Same mode carries out the evaluation of this battery.The results are shown in table 1.
＜ comparative example 2 ＞
As the solvent of electrolyte, use fluoroethylene carbonate and methyl acetate (CAS numbers: Mixed solvent (volume ratio 1:4) 79-20-9).
In addition, in the way of similarly to Example 1, battery is made.Afterwards, with embodiment 1 Same mode carries out the evaluation of this battery.The results are shown in table 1.
＜ comparative example 3 ＞
As the solvent of electrolyte, use fluoroethylene carbonate and methyl propionate (CAS numbers: Mixed solvent (volume ratio 1:4) 554-12-1).
In addition, in the way of similarly to Example 1, battery is made.Afterwards, with embodiment 1 Same mode carries out the evaluation of this battery.The results are shown in table 1.
＜ comparative example 4 ＞
As the solvent of electrolyte, use fluoroethylene carbonate and methyl trimethylacetate (CAS numbers: Mixed solvent (volume ratio 1:4) 598-98-1).
In addition, in the way of similarly to Example 1, battery is made.Afterwards, with embodiment 1 Same mode carries out the evaluation of this battery.The results are shown in table 1.
[table 1]
According to above result, owing to nonaqueous electrolytic solution containing 1-methyl cyclopropane-1-methyl formate, Thus the reliability of battery improves.Think that this effect is owing to having cyclopropyl and the α position at carboxylate There is not hydrogen and realize.
It addition, according to above result, in the case of α position does not have the carboxylate of hydrogen, obtain one The effect that fixed reliability improves.However, it is believed that only by so, the effect that reliability improves is not Fully.
It is therefore contemplated that the effect of the disclosure is to realize by there is cyclopropyl in the α position of carboxylate. That is, by containing the compound shown in above-mentioned formula (1) in the electrolytic solution, it is achieved the effect that reliability improves Really.
It addition, according to embodiment 2 and the result of comparative example 1, even if by a small amount of containing 1-methyl ring Propane-1-methyl formate, it is also possible to improve reliability.
Industrial applicability
The electrolyte of the disclosure can be used as the electrolyte of battery.

Claims (12)

1. an electrolyte, contains:
Nonaqueous solvent and
It is dissolved in the alkali metal salt of described nonaqueous solvent,
Described nonaqueous solvent contains the chain carboxylate shown in following formula (1),
Wherein, R1And R2Separately represent aromatic series base or unsaturated aliphatic base or saturated fat Fat race base.
Electrolyte the most according to claim 1, the described R in described chain carboxylate1And institute State R2It is methyl.
Electrolyte the most according to claim 1, relative to the cumulative volume of described nonaqueous solvent, institute The ratio stating chain carboxylate is 1 more than volume %.
Electrolyte the most according to claim 3, relative to the cumulative volume of described nonaqueous solvent, institute The ratio stating chain carboxylate is 50 more than volume %.
Electrolyte the most according to claim 4, relative to the cumulative volume of described nonaqueous solvent, institute The ratio stating chain carboxylate is 80 more than volume %.
Electrolyte the most according to claim 1, described nonaqueous solvent contains fluoroethylene carbonate.
Electrolyte the most according to claim 1, described alkali metal salt is lithium salts.
Electrolyte the most according to claim 7, described lithium salts is selected from LiBF4、LiPF6、 LiN(SO2CF3)2And LiN (SO2F)2In at least one.
9. a battery, possesses:
Electrolyte described in claim 1；
Positive pole, described positive pole contains can occlusion and the positive active material of release alkali metal ion；And
Negative pole, described negative pole contain can occlusion and discharge described alkali metal ion negative electrode active material or Person contains alkali metal.
Battery the most according to claim 9, described negative pole contains described alkali metal, described alkali Metal is lithium.
11. batteries according to claim 9, described negative pole contains described negative electrode active material, Described negative electrode active material is carbon.
12. batteries according to claim 9, described positive active material for containing selected from nickel, At least one element in cobalt, manganese and the metal-oxide of lithium.
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